Plasma enhanced chemical deposition of conjugated polymer

ABSTRACT

The method of the present invention has the steps of (a) flash evaporating a conjugated material in an evaporate outlet forming an evaporate; (b) passing the evaporate to a glow discharge electrode creating a glow discharge conjugated monomer plasma from the evaporate; and (c) cryocondensing the glow discharge conjugated monomer plasma on a substrate and crosslinking the glow discharge conjugated monomer plasma thereon, wherein the crosslinking results from radicals created in the glow discharge conjugated monomer plasma and achieves self curing.

CROSS REFERENCE TO RELATED APPLICATIONS

This is a continuation-in-part of application Ser. No. 09/811,871 filedon Mar. 19, 2001 which is a continuation-in-part of application Ser. No.09/212,781 filed on Dec. 16, 1998 (now U.S. Pat. No. 6,207,239).

FIELD OF THE INVENTION

The present invention relates generally to a method of making plasmapolymerized conjugated polymer films. More specifically, the presentinvention relates to making a plasma polymerized conjugated polymer filmvia plasma enhanced chemical deposition with a flash evaporated feedsource of a low vapor pressure compound.

As used herein, the term “(meth)acrylic” is defined as “acrylic ormethacrylic”. Also, (meth)acrylate is defined as “acrylate or methacrylate”.

As used herein, the term “cryocondense” and forms thereof refers to thephysical phenomenon of a phase change from a gas phase to a liquid phaseupon the gas contacting a surface having a temperature lower than a dewpoint of the gas.

As used herein, the term “conjugated” refers to a chemical structure ofalternating single and double bonds between carbon atoms in a carbonatom chain.

BACKGROUND OF THE INVENTION

The basic process of plasma enhanced chemical vapor deposition (PECVD)is described in THIN FILM PROCESSES, J. L. Vossen, W. Kern, editors,Academic Press, 1978, Part IV, Chapter IV—1 Plasma Deposition ofInorganic Compounds, Chapter IV—2 Glow Discharge Polymerization, hereinincorporated by reference. Briefly, a glow discharge plasma is generatedon an electrode that may be smooth or have pointed projections.Traditionally, a gas inlet introduces high vapor pressure monomericgases into the plasma region wherein radicals are formed so that uponsubsequent collisions with the substrate, some of the radicals in themonomers chemically bond or cross link (cure) on the substrate. The highvapor pressure monomeric gases include gases of CH₄, SiH₄, C₂H₆, C₂H₂,or gases generated from high vapor pressure liquid, for example styrene(10 torr at 87.4° F. (30.8° C.)), hexane (100 torr at 60.4° F. (15.8°C.)), tetramethyldisiloxane (10 torr at 82.9° F. (28.3° C.)1,3,dichlorotetra-methyldisiloxane) and combinations thereof that may beevaporated with mild controlled heating. Because these high vaporpressure monomeric gases do not readily cryocondense at ambient orelevated temperatures, deposition rates are low (a few tenths ofmicrometer/min maximum) relying on radicals chemically bonding to thesurface of interest instead of cryocondensation. Remission due toetching of the surface of interest by the plasma competes with thereactive depostion. Lower vapor pressure species have not been used inPECVD because heating the higher molecular weight monomers to atemperature sufficient to vaporize them generally causes a reactionprior to vaporization, or metering of the gas becomes difficult tocontrol, either of which is inoperative.

The basic process of flash evaporation is described in U.S. Pat. No.4,954,371 herein incorporated by reference. This basic process may alsobe referred to as polymer multi-layer (PML) flash evaporation. Briefly,a radiation polymerizable and/or cross linkable material is supplied ata temperature below a decomposition temperature and polymerizationtemperature of the material. The material is atomized to droplets havinga droplet size ranging from about 1 to about 50 microns. An ultrasonicatomizer is generally used. The droplets are then flash vaporized, undervacuum, by contact with a heated surface above the boiling point of thematerial, but below the temperature which would cause pyrolysis. Thevapor is cryocondensed on a substrate then radiation polymerized orcross linked as a very thin polymer layer.

The material may include a base monomer or mixture thereof, crosslinkingagents and/or initiating agents. A disadvantage of the flash evaporationis that it requires two sequential steps, cryocondensation followed bycuring or cross linking, that are both spatially and temporallyseparate.

According to the state of the art of making plasma polymerized films,PECVD and flash evaporation or glow discharge plasma deposition andflash evaporation have not been used in combination. However, plasmatreatment of a substrate using glow discharge plasma generator withinorganic compounds has been used in combination with flash evaporationunder a low pressure (vacuum) atmosphere as reported in J. D. Affinito,M. E. Gross, C. A.. Coronado, and P. M. Martin, A Vacuum Deposition OfPolymer Electrolytes On Flexible Substrates. “Paper for Plenary talk inA Proceedings of the Ninth International Conference on Vacuum WebCoating”, November 1995, ed R. Bakish, Bakish Press 1995, pg 20-36., andas shown in FIG. 1a. In that system, the plasma generator 100 is used toetch the surface 102 of a moving substrate 104 in preparation to receivethe monomeric gaseous output from the flash evaporation 106 thatcryocondenses on the etched surface 102 and is then passed by a firstcuring station (not shown), for example electron beam or ultra-violetradiation, to initiate cross linking and curing. The plasma generator100 has a housing 108 with a gas inlet 110. The gas may be oxygen,nitrogen, water or an inert gas, for example argon, or combinationsthereof. Internally, an electrode 112 that is smooth or having one ormore pointed projections 114 produces a glow discharge and makes aplasma with the gas which etches the surface 102. The flash evaporator106 has a housing 116, with a monomer inlet 118 and an atomizing nozzle120, for example an ultrasonic atomizer. Flow through the nozzle 120 isatomized into particles or droplets 122 which strike the heated surface124 whereupon the particles or droplets 122 are flash evaporated into agas that flows past a series of baffles 126 (optional) to an outlet 128and cryocondenses on the surface 102. Although other gas flowdistribution arrangements have been used, it has been found that thebaffles 126 provide adequate gas flow distribution or uniformity whilepermitting ease of scaling up to large surfaces 102. A curing station(not shown) is located downstream of the flash evaporator 106.

In the flash evaporation process using acrylate and/or methacrylate thestarting monomer is a (meth)acrylate monomer (FIG. 1b). When R₁ ishydrogen (H), the compound is an acrylate and when R₁ is a methyl group(CH₃), the compound is a methacrylate. If the group R₂ pendant to the(meth)acrylate group is fully conjugated, the O—C— linkage interruptsthe conjugation and renders the monomer non-conducting. Exposure toelectron beam radiation, or UV in the presence of a photoinitator,initiates polymerization of the monomer by creating free radicals at the(C═C) double bond in the (meth)acrylate linkage. After polymerization,the two (meth)acrylate Double (C═C) bonds, where the cross-linkingoccurred, have been converted to single (C—C) bonds. Thus, thecross-linking step further interrupts the conjugation and makesconductivity impossible.

Therefore, there is a need for an apparatus and method for making plasmapolymerized conjugated polymer layers at a fast rate but that is alsoself curing, preserving the conjugation.

SUMMARY OF THE INVENTION

The present invention is an improved method of plasma polymerizationwherein a conjugated monomer is cured during plasma polymerization.

The present invention may be viewed from two points of view, vis (1) anapparatus and method for plasma enhanced chemical vapor deposition ofconjugated low vapor pressure monomer or a mixture of monomer withparticle materials onto a substrate, and (2) an apparatus and method formaking self-curing conjugated or conductive polymer layers, especiallyself-curing PML polymer layers. As used herein, the term “conjugatedpolymer” or “fully conjugated polymer” is defined as a polymer havingsufficient degree of conjugation to be electrically conductive whendoped. Thus, either the monomer is fully conjugated or the particleseither combine together or crosslink with the monomer in a manner toprovide a “fully conjugated polymer”.

From both points of view, the invention is a combination of flashevaporation with plasma enhanced chemical vapor deposition (PECVD) thatprovides the unexpected improvements of permitting use of low vaporpressure monomer conjugated materials in a PEDVD process and provides aself curing from a flash evaporation process, at a rate surprisinglyfaster than standard PECVD deposition rates.

Generally, the apparatus of the present invention is (a) a flashevaporation housing with a monomer atomizer for making monomer droplets,heated evaporation surface for making an evaporate from the monomerdroplets, and an evaporate outlet, (b) a glow discharge electrodedownstream of the evaporate outlet for creating a glow discharge plasmafrom the evaporate, wherein (c) the substrate is proximate the glowdischarge plasma for receiving and cryocondensing the glow dischargeplasma thereon. All components are preferably within a low pressure(vacuum) chamber.

The method of the present invention has the steps of (a) flashevaporating a liquid conjugated monomer an evaporate outlet forming anevaporate; (b) passing the evaporate to a glow discharge electrodecreating a glow discharge conjugated monomer plasma from the evaporate;and (c) cryocondensing the glow discharge conjugated monomer plasma on asubstrate whereupon condensed glow discharge conjugated monomer plasmaas a liquid begins crosslinking. The crosslinking results from radicalscreated in the glow discharge plasma and achieves self curing.

It is an object of the present invention to provide a method of making aconjugated or conductive polymer.

An advantage of the present invention is that it is insensitive to adirection of motion of the substrate because the deposited conjugatedmonomer layer is self curing. A further advantage is that theconjugation is preserved during curing. In the prior art, the depositedmonomer layer required a radiation curing apparatus so that the motionof the substrate had to be from the place of deposition toward theradiation apparatus and which interfered with conjugation as previouslydiscussed. Another advantage of the present invention is that multiplelayers of materials may be combined. For example, as recited in U.S.Pat. No. 5,547,508 and 5,395,644, 5,260,095, hereby incorporated byreference, multiple polymer layers, alternating layers of polymer andmetal, and other layers may be made with the present invention in thevacuum environment.

The subject matter of the present invention is particularly pointed outand distinctly claimed in the concluding portion of this specification.However, both the organization and method of operation, together withfurther advantages and objects thereof, may best be understood byreference to the following detailed description in combination with thedrawings wherein like reference characters refer to like elements.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1a is a cross section of a prior art combination of a glowdischarge plasma generator with inorganic compounds with flashevaporation.

FIG. 1b is a chemical diagram of (meth)acrylate.

FIG. 1c is a chemical diagram of phenylacetylene and two plasmapolymerization routes from phenylacetylene to conjugated polymer.

FIG. 1d is a chemical diagram of triphynyl diamine derivitive

FIG. 1e is a chemical diagram of quinacridone.

FIG. 2 is a cross section of the apparatus of the present invention ofcombined flash evaporation and glow discharge plasma deposition.

FIG. 2a is a cross section end view of the apparatus of the presentinvention.

FIG. 3 is a cross section of the present invention wherein the substrateis the electrode.

DESCRIPTION OF THE PREFERRED EMBODIMENT(S)

According to the present invention, the apparatus is shown in FIG. 2.The apparatus and method of the present invention are preferably withina low pressure (vacuum) environment or chamber. Pressures preferablyrange from about 10⁻¹ torr to 10⁻⁶ torr. The flash evaporator 106 has ahousing 116, with a monomer inlet 118 and an atomizing nozzle 120. Flowthrough the nozzle 120 is atomized into particles or droplets 122 whichstrike the heated surface 124 whereupon the particles or droplets 122are flash evaporated into a gas or evaporate that flows past a series ofbaffles 126 to an evaporate outlet 128 and cryocondenses on the surface102. Cryocondensation on the baffles 126 and other internal surfaces isprevented by heating the baffles 126 and other surfaces to a temperaturein excess of a cryocondensation temperature or dew point of theevaporate. Although other gas flow distribution arrangements have beenused, it has been found that the baffles 126 provide adequate gas flowdistribution or uniformity while permitting ease of scaling up to largesurfaces 102. The evaporate outlet 128 directs gas toward a glowdischarge electrode 204 creating a glow discharge plasma from theevaporate. In the embodiment shown in FIG. 2, the glow dischargeelectrode 204 is placed in a glow discharge housing 200 having anevaporate inlet 202 proximate the evaporate outlet 128. In thisembodiment, the glow discharge housing 200 and the glow dischargeelectrode 204 are maintained at a temperature above a dew point of theevaporate. The glow discharge plasma exits the glow discharge housing200 and cryocondenses on the surface 102 of the substrate 104. It ispreferred that the substrate 104 is kept at a temperature below a dewpoint of the evaporate, preferably ambient temperature or cooled belowambient temperature to enhance the cryocondensation rate. In thisembodiment, the substrate 104 is moving and may be electricallygrounded, electrically floating or electrically biased with an impressedvoltage to draw charged species from the glow discharge plasma. If thesubstrate 104 is electrically biased, it may even replace the electrode204 and be, itself, the electrode which creates the glow dischargeplasma from the monomer gas. Electrically floating means that there isno impressed voltage although a charge may build up due to staticelectricity or due to interaction with the plasma.

A preferred shape of the glow discharge electrode 204, is shown in FIG.2a. In this preferred embodiment, the glow discharge electrode 204 isseparate from the substrate 104 and shaped so that evaporate flow fromthe evaporate inlet 202 substantially flows through an electrode opening206. Any electrode shape can be used to create the glow discharge,however, the preferred shape of the electrode 204 does not shadow theplasma from the evaporate issuing from the outlet 202 and its symmetry,relative to the monomer exit slit 202 and substrate 104, providesuniformity of the evaporate vapor flow to the plasma across the width ofthe substrate while uniformity transverse to the width follows from thesubstrate motion.

The spacing of the electrode 204 from the substrate 104 is a gap ordistance that permits the plasma to impinge upon the substrate. Thisdistance that the plasma extends from the electrode will depend on theevaporate species, electrode 204/substrate 104 geometry, electricalvoltage and frequency, and pressure in the standard way as described indetail in ELECTRICAL DISCHARGES IN GASSES, F. M. Penning, Gordon andBreach Science Publishers, 1965, and summarized in THIN FILM PROCESSES,J. L. Vossen, W. Kern, editors, Academic Press, 1978, Part II, ChapterII-1, Glow Discharge Sputter Deposition, both hereby incorporated byreference.

An apparatus suitable for batch operation is shown in FIG. 3. In thisembodiment, the glow discharge electrode 204 is sufficiently proximate apart 300 (substrate) that the part 300 is an extension of or part of theelectrode 204. Moreover, the part is below a dew point to allowcryocondensation of the glow discharge plasma on the part 300 andthereby coat the part 300 with the monomer condensate and self cure intoa polymer layer. Sufficiently proximate may be connected to, restingupon, in direct contact with, or separated by a gap or distance thatpermits the plasma to impinge upon the substrate. This distance that theplasma extends from the electrode will depend on the evaporate species,electrode 204/substrate 104 geometry, electrical voltage and frequency,and pressure in the standard way as described in ELECTRICAL DISCHARGESIN GASSES, F. M. Penning, Gordon and Breach Science Publishers, 1965,hereby incorporated by reference. The substrate 300 may be stationary ormoving during cryocondensation. Moving includes rotation and translationand may be employed for controlling the thickness and uniformity of themonomer layer cryocondensed thereon. Because the cryocondensation occursrapidly, within milli-seconds to seconds, the part may be removed aftercoating and before it exceeds a coating temperature limit.

In operation, either as a method for plasma enhanced chemical vapordeposition of low vapor pressure conjugated materials onto a substrate,or as a method for making self-curing conjugated polymer layers(especially PML), the method of the invention has the steps of (a) flashevaporating a conjugated material forming an evaporate; (b) passing theevaporate to a glow discharge electrode creating a glow dischargeconjugated monomer plasma from the evaporate; and (c) cryocondensing theglow discharge conjugated monomer plasma on a substrate and crosslinkingthe glow discharge conjugated monomer plasma thereon. The crosslinkingresults from radicals created in the glow discharge plasma therebypermitting self curing.

The flash evaporating has the steps of flowing a conjugated material toan inlet, atomizing the conjugated material through a nozzle andcreating a plurality of conjugated monomer droplets of the conjugatedmonomer liquid as a spray. The spray is directed onto a heatedevaporation surface whereupon it is evaporated and discharged through anevaporate outlet.

The liquid conjugated material may be any liquid conjugated monomer.However, it is preferred that the liquid conjugated monomer or liquidhave a low vapor pressure at ambient temperatures so that it willreadily cryocondense. Preferably, the vapor pressure of the liquidconjugated monomer material is less than about 10 torr at 83° F. (28.3°C.), more preferably less than about 1 torr at 83° F. (28.3° C.), andmost preferably less than about 10 millitorr at 83° F. (28.3° C.). Forconjugated monomers of the same chemical family, conjugated monomerswith low vapor pressures usually also have higher molecular weight andare more readily cryocondensible than higher vapor pressure, lowermolecular weight conjugated monomers. Liquid conjugated monomer includesbut is not limited to phenylacetylene (FIG. 1c).

Alternatively, the conjugated material may be an unconjugated monomercontaining conjugated particles or a conjugated monomer with conjugatedparticles. Unconjugated monomers include but are not limited to(meth)acrylate(s) and combinations thereof.

The conjugated particle(s) may be any insoluble or partially insolubleconjugated particle type having a boiling point below a temperature ofthe heated surface in the flash evaporation process. Insolubleconjugated particle includes but is not limited to phenyl acetylenetriphenyl diamine derivative (TPD, FIG. 1d), quinacridone (QA, FIG. 1e)and combinations thereof. To achieve a conductive polymer it isnecessary to dope a conjugated polymer. Doping is with a salt includingbut not limited to lithium-trifluoromethanesulfonate (CF₃SO₃Li), othersalts of lithium, salts of iodine, iodine and combinations thereof.

The insoluble conjugated particles are preferably of a volume much lessthan about 5000 cubic micrometers (diameter about 21 micrometers) orequal thereto, preferably less than or equal to about 4 cubicmicrometers (diameter about 2 micrometers). In a preferred embodiment,the insoluble conjugated particles are sufficiently small with respectto particle density and liquid monomer density and viscosity that thesettling rate of the conjugated particles within the liquid monomer isseveral times greater than the amount of time to transport a portion ofthe particle liquid monomer mixture from a reservoir to the atomizationnozzle. It is to be noted that it may be necessary to stir theconjugated particle liquid monomer mixture in the reservoir to maintainsuspension of the conjugated particles and avoid settling.

The mixture of monomer and insoluble or partially soluble conjugatedparticles may be considered a slurry, suspension or emulsion, and theconjugated particles may be solid or liquid. The mixture may be obtainedby several methods. One method is to mix insoluble conjugated particlesof a specified size into the monomer. The insoluble conjugated particlesof a solid of a specified size may be obtained by direct purchase or bymaking them by one of any standard techniques, including but not limitedto milling from large conjugated particles, precipitation from solution,melting/spraying under controlled atmospheres, rapid thermaldecomposition of precursors from solution as described in U.S. Pat. No.5,652,192 hereby incorporated by reference. The steps of U.S. Pat. No.5,652,192 are making a solution of a soluble precursor in a solvent andflowing the solution through a reaction vessel, pressurizing and heatingthe flowing solution and forming substantially insoluble conjugatedparticles, then quenching the heated flowing solution and arrestinggrowth of the conjugated particles. Alternatively, larger sizes of solidconjugated material may be mixed into liquid monomer then agitated, forexample ultrasonically, to break the solid conjugated material intoconjugated particles of sufficient size.

Liquid conjugated particles may be obtained by mixing an immiscibleconjugated liquid with the monomer liquid and agitating by ultrasonic ormechanical mixing to produce liquid conjugated particles within theliquid monomer. Immiscible conjugated liquids include, for examplephenylacetylene.

Upon spraying, the droplets may be conjugated particles alone,conjugated particles surrounded by liquid monomer and liquid monomeralone. Since both the liquid monomer and the conjugated particles areevaporated, it is of no consequence either way. It is, however,important that the droplets be sufficiently small that they arecompletely vaporized. Accordingly, in a preferred embodiment, thedroplet size may range from about 1 micrometer to about 50 micrometers.

By using flash evaporation, the conjugated material is vaporized soquickly that reactions that generally occur from heating a liquidconjugated material to an evaporation temperature simply do not occur.Further, control of the rate of evaporate delivery is strictlycontrolled by the rate of conjugated material delivery to the inlet 118of the flash evaporator 106.

In addition to the evaporate from the conjugated material, additionalgases may be added within the flash evaporator 106 through a gas inlet130 upstream of the evaporate outlet 128, preferably between the heatedsurface 124 and the first baffle 126 nearest the heated surface 124.Additional gases may be organic or inorganic for purposes included butnot limited to ballast, reaction and combinations thereof. Ballastrefers to providing sufficient lecules to keep the plasma lit incircumstances of low evaporate flow rate.

Reaction refers to chemical reaction to form a compound different fromthe evaporate. Additional gases include but are not limited to groupVIII of the periodic table, hydrogen, oxygen, nitrogen, chlorine,bromine, polyatomic gases including for example carbon dioxide, carbonmonoxide, water vapor, and combinations thereof.

The conjugated polymer is conductive when doped with a dopant forexample a salt of iodine, lithium or a combination thereof. The dopantis preferably introduced into the conjugated monomer and carried overwith the conjugated monomer during flash evaporation.

Alternative Embodiments

The method of the present invention may obtain a polymer layer either byradiation curing or by self-curing. In radiation curing (FIG. 1), themonomer liquid may include a photoinitiator. In self-curing, a combinedflash evaporator, glow discharge plasma generator is used without eitherthe e-beam gun or ultraviolet light.

CLOSURE

While a preferred embodiment of the present invention has been shown anddescribed, it will be apparent to those skilled in the art that manychanges and modifications may be made without departing from theinvention in its broader aspects. The appended claims are thereforeintended to cover all such changes and modifications as fall within thetrue spirit and scope of the invention.

I claim:
 1. A method of making a conjugated polymer layer with plasmaenhanced chemical vapor deposition of a conjugated material onto asubstrate in a vacuum environment, comprising: (a) making an evaporateby receiving said conjugated material into a flash evaporation housing,evaporating said conjugated material on an evaporation surface, anddischarging an evaporate of said conjugated material through anevaporate outlet; (b) making a monomer plasma from said evaporate bypassing said evaporate proximate a glow discharge electrode; and (c)cryocondensing said monomer plasma onto said substrate; wherein saidconjugated material is a conjugated monomer or an unconjugated monomerwith conjugated particles or said conjugated monomer with saidconjugated particles.
 2. The method as recited in claim 1, wherein thesubstrate is proximate the glow discharge electrode and is electricallybiased with an impressed voltage, and wherein the monomer plasmacryocondenses on said substrate.
 3. The method as recited in claim 1,wherein said glow discharge electrode is positioned within a glowdischarge housing having an evaporate inlet proximate the evaporateoutlet, said glow discharge housing and said glow discharge electrodemaintained at a temperature above a dew point of said evaporate, saidsubstrate being downstream of said monomer plasma and electricallyfloating, and wherein the monomer plasma cryocondenses on saidsubstrate.
 4. The method as recited in claim 1, wherein the substrate isproximate the glow discharge electrode and is electrically grounded, andwherein the monomer plasma cryocondenses on said substrate.
 5. Themethod as recited in claim 1, wherein said substrate is cooled.
 6. Themethod as recited in claim 1, further comprising adding an additionalgas within said flash evaporation housing.
 7. The method as recited inclaim 6, wherein said additional gas is a ballast gas.
 8. The method asrecited in claim 6, wherein said additional gas is a reaction gas. 9.The method as recited in claim 1, further comprising adding a dopant tosaid conjugated material.
 10. The method as recited in claim 9, whereinsaid dopant is selected from the group consisting of iodine, salts ofiodine, salts of lithium, and combinations thereof.
 11. The method asrecited in claim 1, wherein said conjugated particles are selected fromthe group consisting of organic solids, organic liquids, andcombinations thereof.
 12. The method as recited in claim 1, furthercomprising the step of adding a dopant to said conjugated material sothat said conjugated polymer layer is an electrically conductivepolymer.
 13. A method for making conjugated polymer layers in a vacuumchamber, comprising: (a) flash evaporating a conjugated material formingan evaporate; (b) passing said evaporate to a glow discharge electrodecreating a glow discharge conjugated monomer plasma from the evaporate;and (c) condensing said glow discharge conjugated monomer plasma on asubstrate as a condensed conjugated monomer layer and crosslinking saidcondensed conjugated monomer layer thereon, said crosslinking resultingfrom radicals created in said glow discharge conjugated monomer plasma.14. The method as recited in claim 13, wherein the substrate isproximate the glow discharge electrode and is electrically biased withan impressed voltage, and wherein the monomer plasma cryocondenses onsaid substrate.
 15. The method as recited in claim 13, wherein said glowdischarge electrode is positioned within a glow discharge housing havingan evaporate inlet proximate the evaporate outlet, said glow dischargehousing and said glow discharge electrode maintained at a temperatureabove a dew point or said evaporate, said substrate being downstream ofsaid conjugated monomer plasma and electrically floating, and whereinthe monomer plasma cryocondenses on said substrate.
 16. The method asrecited in claim 13, wherein the substrate is to proximate the glowdischarge electrode and is electrically grounded, and wherein themonomer plasma cryocondenses on said substrate.
 17. The method asrecited in claim 13, wherein said conjugated material is a conjugatedmonomer.
 18. The method as recited in claim 13, wherein said substrateis cooled.
 19. The method as recited in claim 13, further comprisingadding a dopant to said conjugated material.
 20. The method as recitedin claim 19, wherein said dopant is selected from the group consistingof iodine, salts of iodine, salts of lithium, and combinations thereof.21. The method as recited in claim 19, wherein said conjugated materialis a monomer containing conjugated particles.
 22. The method as recitedin claim 13, wherein said monomer is a conjugated monomer.
 23. Themethod as recited in claim 21, wherein said conjugated particles areselected from the group consisting of organic solids, organic liquids,and combinations thereof.